AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

.....2......................4 Control parameters in the volumetric KF titration .....3...............1 The Control Band ..............1 Filling the coulometric cell .............4 Generator electrode without diaphragm ........3 Iodine generation..........2..............1....1 Indication ......................1............................................................39 1 .................................10 2...........................................................................................12 3 Titration control and end point determination.... The Karl Fischer titration.......7 2...................................................6 General recommendations ...............METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration .................11 2...........................0 mg/g ......................2 When do you have to replace the electrolyte? .......................18 3..........................2.................................8 2..........................................28 4.4...............2 The Karl Fischer chemical reaction ....................................3 Concentration determination with Water Standard 10..................................21 3......................................................................................................................28 4....................................1...........................................................19 3..........................................................................1 KF coulometry .................2 The minimum and maximum dosing rate .....26 4...1 Volumetric KF reagents.......................................4 Concentration determination with pure water...1.4.....27 4.....38 5 Sampling ...........................6 Termination parameters for both coulometric and volumetric KF titration..........................................................3...........2 The drift .5 1.....................................................3..............................1 The influence of atmospheric humidity (drift determination) ............................24 4.....29 4...............4 1..........4..............................6 Dissolving capacity of the solvent ...........................7 2........................................11 2...................................................................33 4........................9 2...............2 End point and polarization current......26 4..........................................................3 The Cautious start ....9 2..........................3 Consequences for practical applications................22 3..........2...........13 3......................................................................1 Principle of bipotentiometric indication ...................1...................26 4.............2 Coulometric KF analysis............................................................14 3..............................4 Polarization current and end point................................................................1 One-component KF reagent ...................................4 1...................................................................................................4..............................................................................................................................1..............................................................8 2................................................................2..........................................6............3..........................................................................................................................1 How often should the concentration be determined?.......................1..............16 3...............3................9 2...2 Two-component KF reagent .........3 Secure draining and filling of the titration cell: SOLVENT MANAGER........................36 4..........................3 Stirring speed and dispersion of the volumetric KF titrant.................5 Cleaning the measuring electrode ....................................7 2..............................1 Titration stand ........................2......29 4..........6 2 Volumetric and Coulometric Karl Fischer Analyses .........5 The solvent............21 3.....................13 3...........................................2 Working with the coulometric KF instruments .......3 Volumetric KF Titration: Titrant concentration............................5 Application tips ........................5 Karl Fischer reagents with ethanol ..................32 4.....................................33 4...........................37 4................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ..........................................................13 3...................4.....1...............2....1 An historic overview .........................20 3.....2..........2.....34 4...........................................1..5 Control paramaters in the coulometric KF Analysis ........................................3...........................................................................................................33 4.........................5 Limitations for the use of the cell without diaphragm..........19 3.8 2....4.........................4 Special reagents for aldehydes and ketones......................................35 4...........2 Concentration determination with di-sodium tartrate dihydrate..................4 Cleaning the coulometric KF titration cell...............2.........................18 3....................................................................3 Pyridine-containing reagents ...2 Reaction rate ................................................................2 Stoichiometry of the coulometric KF rection ....16 3.............................................................................................................................19 3.

.....................................................................................................................83 11..............78 11.............2..67 8...1 Organic and inorganic chemicals .......4 Liquids: Sample input.........................................2 Solid samples....2 Inorganic chemicals ..................................87 11...................................................................................58 7.....6.......................70 9...........................5 Accessories for sample input ...73 10.......................86 11.......................71 9......................70 9................................................................3 External dissolution .....................................2 Storing the sample ............89 12 Appendix ........................................73 10..............1 Internal extraction .......1 Volumetric methods .......................................................................................................1............5 Determination of water in gases ........2 Purge gas...................5 Additional literature ...1...............................................................4...............................................................................................................................................................................................................................3................................4 Technical products ..........................1 Reaction with methanol..............................1 Coulometry.....6 Food ...................................................43 6.......................................88 11............2 Measurement accuracy.62 8 Measurement results ...................................................................................................................................................................4...............................................................................1...........................3......................6.....................................................55 7..58 7..............................................................................................................................................................86 11...................................................6...............2 Reaction with water.................................4....70 9...........................................................inorganic ................86 11.....................................1.....................................................................................78 11.........................................................47 7................................................................................43 6.............................2..................................................................................................3 Repeatability .....6........................................................60 7....90 2 ......................................................................................79 11...............................................................................................................................1 Resolution and detection limit ................79 11...........................3 Liquids: Characteristics .............................................................2 Solids: Sample input .........................72 10 Troubleshooting ..................................................81 11..............79 11..........4.................2 Coulometric methods ....................................................67 8............................................................................................................................................................77 11.................................71 9....................1 Principle .................................................................................1.........................3 Procedure....................3 Titration Methods ...............85 11...............1 Organic Chemicals.......83 11...........59 7.................................................................................................................2 External extraction ...............................................6 Determination using the drying oven ......71 9......1 Effects of temperature.....................................3 Technical products – organic ...57 7..................................................................................................................................................................1.................................................................................................................................................................................6.....................80 11.............................................2..............................................................80 11........................3 Reaction with iodine .............................2 Side reactions ......................................5 Technical natural products ......4 Manual Karl Fischer drying oven........................................................49 7..................................................................................................2.........................................45 7 Release of water from the sample ..............................................................77 11.........................................75 11 Karl Fischer Titration: The Method at a Glance ........4.48 7..................40 6 Sample addition .............................67 8.................77 11..2 Volumetric Karl Fischer Titration ..........................................................................................................39 5.........................................................................54 7.............2 Foods and technical products .........................................................................4 Lyophilized substance in septum bottles.................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5...6 References...........2 Liquid samples .............................58 7......................4 Example: reevaluation of side reactions ...............................5 STROMBOLI automatic oven sample changer ...........................................................................................1 Solids: Characteristics.........................................................................................................................68 9 Interferences ...............................................................................1 Taking the sample...39 5..............................87 11.........................................................................4 Sample preparation and input .......1 Solid samples........................4.......................................................................................3 Amount of sample ................87 11...........1 Liquid samples ...........................

................................4.........98 3 ...........................................................................................95 12.........3 Standards for Karl Fischer coulometry.................96 12.....94 12...6 Titrants and solvents for volumetric analysis ......................................2 Formula for the external dissolution ...................................................................................93 12.......................................2 For samples that are poorely soluble in methanol or ethanol .................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12......................................................................1 One-component reagent .....91 12......................5 For acids and bases (pH value) ..........92 12...................96 12.................98 13.......................1 Formula for the external extraction ...........4 Reagents and solvents for coulometric analysis ....................6................................................6..............................3 For samples that are insoluble in methanol or ethanol ..........98 13......4..4 Safety data for the KF-components and auxiliary solvents: ...........97 13 Hazards and waste disposal tips ..........................5 Water Standards for Karl Fischer volumetric titration.......95 12......................2 Two-component reagent: ....................................................93 12...4.............................3 Reagents for coulometry: ................................4...................................1 For samples soluble in methanol or ethanol ..........3 For samples insoluble in methanol or ethanol..................................................................6.........................................................4...............................................98 13....................92 12..92 12...........95 12........................................................................95 12..............................6...........................5 For acids and bases (pH value) ..........................................................................................................................90 12.........6...............1 For samples that are soluble in methanol or ethanol ...91 12..................2 For samples poorly soluble in methanol or ethanol..................4 For ketones and aldehydes......98 13.....4 For ketones and aldehydes.....

D. First German DIN standard for the Karl Fischer titration (DIN 51777.5% and 1%. Wernimont and F. Jungnickel. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58.0. Automatic KF titration instruments with piston motorized burettes. respectively. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. First diaphragm-less cell for coulometric KF titration. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. 1.Direct method”). 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1.0. S. Solid KF Oven Standards with water contents of 5. Water standards (10. Eberius [3]. Use of Karl Fischer method spreads. and solvent dispensing and removal. Pyridine-free KF reagents are commercially available. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. titrant specific standard parameters and LEARN titration.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. Enormous spread of the use of KF titration. Publication: “The Dead-Stop End Point“. promoted by publications by E. First coulometric KF titration instruments are commercially available. Publication: Coulometric Karl Fischer Titration by A. April 1956. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation.Boyd [4]. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. DL37 KF Coulometer from METTLER TOLEDO. They replaced the DL18/35 KF Volumetric Titrators. L. M. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm).J. Hopkinson [2]. Introduction of less poisonous KF reagents based on ethanolic solution. Meyer and C. Publication on stabilized single-component Karl Fischer reagent by E. 2000 2001 2002 2008 4 . “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. Peters and J.1 mg/g) with test certificate according to DIN 50049-2. by G.

Bryanz and Mitchell [6] formulated a two-step reaction: 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). At pH values above 8. Methanol proved to be suitable as a solvent. In an alcohol-free solution. the 5 .. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. W. and the faster the rate of the Karl Fischer reaction. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. methanol not only acts as a solvent but also participates directly in the reaction itself. described by the rate constant k. Verhoff and E. the more methyl sulfite is formed by the capture of protons. The rate of the Karl Fischer reaction.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. Karl Fischer used pyridine for this purpose. C. Smith. I2 + SO2 + 3 Py + H2O → 2.5 to 8. i. In order to achieve an equilibrium shift to the right. the maximum reaction rate is reached here and cannot increase further.e. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. it only acts as a buffering agent and can therefore be replaced by other bases.5. all the sulfur dioxide is present as methyl sulfite. In an alcoholic solution. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. I2 + SO2 + 3 Py + H2O → 2. In the pH range 5. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. but rather the methyl sulfite ion. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1].

methanol) (e. you can use other alkohols such as. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. ethylene glycol monomethyl ether. This improves the titer stability.g.g. ethanol. diethylene glycol monoethylether) [10. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more.g. If a methanol-free titrant has to be used (e. for instance.g. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. and for bases: salicylic acid). This reagent not only replaced the toxic. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. pH values less than 4 and greater than 8 should be avoided in practice. 2-propanol. methoxyethanol. In 1988. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. 6 . pungent pyridine.C. this results in a more sluggish endpoint and higher iodine consumption. Verhoff and E. On the basis of this knowledge. Studies by E. With acidic or basic samples. J. is not a serious limitation because the water concentration in the solvent is usually much less. and references therein]. Methanol should therefore always be present in the minimum required amount. for determination in ketones or aldehydes). Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. however.5 to 8. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. A. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. This. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. E. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5. ROH + SO2 + RN 2. in a titration.

. Coulometric Karl Fischer Analysis. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. The reagent can be stored for approximately two years. Suitable for samples where water is present as a major component: 100 ppm . the decrease in concentration.1 Volumetric KF reagents 2. sulfur dioxide and imidazole.e. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. 2 mg/mL for samples with a water content of less than 1000 ppm.5% 2. is approximately 0. dissolved in a suitable alcohol. The drop in titer. i. Suitable for samples where water is present in trace amounts: 1 ppm . You can also use a methanolic solvent mixture specially adapted to the sample as the solvent.1 One-component KF reagent The titrant contains iodine.5 mg/mL per year in a sealed bottle. 1 mg/mL for samples with a water content of less than 200 ppm. 7 .1. where a solution containing iodine is added using a motorized piston burette.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. The solvent is methanol.

A titration speed two or three times as high can be achieved with the two-component reagent. reagents containing pyridine are still used because they are cheaper and can be made in-house. imidazole.g.g. favorably priced.1.2 Two-component KF reagent The titrant contains iodine and methanol. + Simple handling. – Titer less stable. and results in higher titration speed.1. One-component reagent: The titrant contains iodine. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. The separation into titrant and solvent improves stability of the KF reagents. Solvent capacity restricted. sulfur dioxide and 2-methoxyethanol. imidazole and methanol. sulfur dioxide and pyridine. methanol) and B (iodine. e. Two-component reagent: The titrant contains iodine dissolved in an alcohol. additional water is produced and titrated at the same time. Reagents One-component Two-component 2. Special methanol-free KF one-component reagents such as e. 8 . dissolved in an alcohol (usually methanol). leading to higher water contents and a vanishing end point. whereas the solvent consists of sulfur dioxide and a base. stable titer. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. pyridine. HYDRANAL® (Composite 5K and Working Medium K. dissolved in methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. The solvent is either methanol or consists of methanol mixtures. These solutions are mixed 1:1 just before use to form the one-component titrant. High titration speed. The titrant has a stable titer. This reagent is declared as “rapid”. The solvent contains sulfur dioxide. which allow for fast and accurate Karl Fischer titrations.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. whereas the solvent contains 2-chloroethanol and trichloromethane. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. increases their lifetime. To improve stability. methanol). This special reagent is also suitable for substances that react with methanol. Both the components are very stable in storage. from VWR/MERCK) are commercially available to prevent this problem.1. Note that it may be necessary to adapt the end point value in the titration method to these reagents.g. 2. 2 mg/mL for samples with a water content of less than 1000 ppm.g. e. One-component reagent: The titrant contains iodine. As a result. titration speed slower. or an alcoholic mixture. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. from Sigma-Aldrich) and e. provided that the bottle is tightly sealed. imidazole. methanol. such as amines. The titration takes slightly longer than with the standard KF reagent.

2 Coulometric KF analysis 2. Both parts are separated by a diaphragm. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry.1. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. a double pin platinum electrode. the anode compartment and the cathode compartment. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . two-component. 2. 9 . however.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. The generator is close to the measuring electrode*. imidazole. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. or “inner burette”) incorporated into the glass titration cell.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. The titrant contains iodine and ethanol. The classical coulometric cell consists of two parts.2. whereas the solvent contains sulfur dioxide. diethanolamine and ethanol. ethanol-based reagents were launched in 1998.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.

To avoid this. Subsequently. CH3SO3H. or the same reagent as used in the anode compartment. releasing two electrons at the anode. Note that methyl sulfonic acid.e. as chloroform. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. This can cause the cathode to become black. i. imidazole and iodide salts. other solvents such e. This consists of sulfur dioxide. Cathode reaction At the cathode. 2. Anode reaction At the anode. The value 96845 C/mol is known as the Faraday constant. which subsequently reacts with water. 96485 C of current are needed.2.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. To calculate it.→ I2 → H2O 10 . I-. The negative iodide ions release electrons at the anode and form iodine.g. hexanol or ethylene glycol may be added. C. are oxidized to one molecule of iodine. Methanol or ethanol is used as solvent. 2 I. used to generate iodine. In Karl Fischer reaction two iodide ions.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. the catholyte should be replaced once in two weeks. present in the anolyte compartment. it is necessary to first recall the definition of 1 Coulomb: one coulomb. i. the positive hydrogen ions are reduced to hydrogen. The catholyte is either a manufacturer-specific special reagent. iodine reacts with water. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. An ammonium salt is added to the catholyte in order to promote hydrogen production. it is known that to produce one mole of a chemical substance that requires one electron. The cathode compartment contains the catholyte. 1C=1A·1s On the other hand.e. octanol. is the quantity of charge that is transported by a current of 1 ampere in one second. I2. iodine is generated from iodide by electrochemical oxidation. This is the main product formed.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. Depending on the application. 2 [RN]H+ + 2e. C.

300. 2. Since current and time can be accurately measured. no standardization of the coulometric KF reagents is necessary. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard.2. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. For this reason.e. it is used as a reference method for the determination of water content. coulometry is designated as absolute method. Nevertheless. hexanol. the maximum possible current applied by the instrument is 100 mA. As a consequence. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. With standard conductivity values. the current conversion efficiency for iodine production is assumed to be 100%.015 g/mol.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989.). 2 x 96485 C/mol is required for 1 mole of water. etc. the coulometer operates with current pulses of 400 mA. Since the molar mass of water is 18. 2. For an electrochemically optimized Karl Fischer cell.712 C electrical current. At very low conductivities (i. 200 and 100 mA. In addition. less than 3–4 μS/cm).2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore.3 Iodine generation Iodine is generated by means of current pulses of 400.

the relative error due to this effect can be minimized by using a larger amount of sample.ethers ketones (with special reagent) . this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. 12 .chlorinated hydrocarbons alcohols .phenols (most) esters . and for very accurate determinations.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. In practice. This is a very good reducing agent. This effect is further enhanced by the small dimensions of the cathode. for measurement of samples having a very low water content (e. the cell with diaphragm may yield more precise results. etc.e. it is still possible for a very small amount of iodine to reach the cathode. especially for nitro compounds such as nitrobenzene. especially when easily reducible. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally.g.2.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. 2. other easily reducible substances such as unsaturated fatty acids. Nascent hydrogen is formed at the cathode. the cathode is a small-size pin). Thus. However. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. To avoid this concurring reaction.. may also be reduced at the cathode by the formation of water. In addition. a different geometry is used for the generating cell without diaphragm. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. Nevertheless. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. lower than 50 μg water/sample).acetamides etheric oils and essences . R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. The latter can thus react more efficiently with water.

the reaction rate of the Karl Fischer reaction . Ideally.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). the water content. the titration is terminated. • • As long as the added iodine reacts with the water. When the voltage drops below a defined value.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled.the control algorithm and its parameters. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. A high voltage is necessary to maintain the specified polarization current at the electrode. 13 . A small.the viscosity of the solution and its temperature. 3.1. there is no free iodine in the titration/anolyte solution. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. . . iodine should be added or generated as quickly as possible.1 Indication 3. • • • As soon as all the water has reacted with iodine. The resulting titration speed depends on the following factors: .the addition speed or generation rate of iodine . Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant.the stirring speed and mixing of the sample solution. The control of the titration is only possible if the end point is indicated. and the addition or production stopped exactly at the end point. and hence. . there will be free iodine in the titration solution.the termination of the analysis.

The iodine is present only at low concentration. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. Above all.the polarization current. The end point value mainly depends on . the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-).e. The two negatively charged iodide ions are attracted by the positively charged platinum pin. again. 14 . A voltage of ca.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. . free iodine is present in the titration/anolyte solution. This drop in voltage is used to indicate the end of the titration. This free iodine gives rise to "ionic conduction". this value depends on the polarization current. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction".1. I2. 3.the solvent or anolyte used in the instrument. It then acquires two electrons and turns into iodide ions (2 I–). where they donate the electrons and form an iodine molecule. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. If mixing is poor. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. which are present in excess in the titration solution. respectively. i.(to a lesser extent) the type of electrode (i.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell.e. Ipol . • • At the beginning and during the titration: As long as the iodine generated reacts with the water. no iodine reaches the negatively charged platinum pin. there is no free iodine in the titration/anolyte solution. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. Iodide ions. geometry and dimensions of the metal parts) .

e. As a consequence. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. This makes it more difficult to stop the titration at the right moment. iodine excess should be as low as possible to get accurate results. Sensors with short platinum pins (< 3 mm). a layer is formed on the surface of the platinum pin sensor. exhibit a larger potential jump and also a higher end point. i. On the other hand. the polarization current should be set as low as possible. pin length: 3 to 4 mm. just after the equivalence point.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. The larger the diameter of the pipe. and increases the sensor resistance. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. Sensors with a large platinum surface. With use. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). and increases the risk of over titration. with longer pins. a double ring or plates instead of rings. and subsequently it remains constant. exhibit a smaller potential jump. on the other hand. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. However. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. its surface can easily bond suitable chemical compounds.g. In general the larger the platinum surface the smaller the current density. e. pin length: 3 . With used sensors. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis.4 mm. 15 . a lower polarization current gives a smaller and steeper potential jump at the end of the titration. i. The layer is formed during the first ten titrations.e. The current density can be compared to a water pipe where a specific water has to flow.

the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction.2 min with a titrant consumption of 2. [H2O] . It is consumed with each additional measured sample leading to a decreasing dioxide concentration.and on the iodine concentration. lower reaction rates are achieved with anolyte solutions that have been used for a long time.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition.0 mL In the coulometric KF analysis. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. stirring speed. shape of the vessel (volumetric KF titration).5 . the water content is high. and overtitration may occur. [SO2] .2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. sulfur dioxide is present in large excess in the anolyte. At the beginning. [I2] .3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. irregular. On the other hand. If the speed is too slow. 3. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. In the volumetric KF titration. 2.0 mL 1. Mixing is influenced by the 1. the titration may also be too slow. Iodine generation or addition is usually the rate determining factor. point of titrant addition (volumetric KF titration). Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. a large excess of sulfur dioxide is present in the solvent. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. with the twocomponent reagents. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. the water concentration is lower. As a consequence.the sulfur dioxide concentration. 3. If 16 . which gives a high reaction rate.the water concentration. Towards the end of the titration. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2.

the stirring speed is too fast. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. 17 . Otherwise the sensor may directly detect added iodine. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. Iodine would not be distributed upwards. but rather along the base directly towards the sensor. This is essential for a fast reaction rate and for short titration times. Bubbles falsify the measured values. leading to slower addition and longer titration time. turbulence is not achieved and the mixing effectiveness is lower.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. Furthermore. If a longer stirring bar is used.

4.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal. The dynamic behaviour of the control can be influenced by a variation of the control band. The following drawing reveals a schematical illustration of the control band: 18 .1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.

. e. Dosing rate (max) = 2 mL/min. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. sensors with very short platinum pins (< 3 mm).4.4. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. the slower is the titrant addition. Thus.4 Polarization current and end point Each end point is valid for a specific polarization current. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. The closer the potential to the end point. the titration starts with a slower acceleration (ramp up) than in the normal mode.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. the titration will take too long. the titrator automatically issues a warning. In particular. at higher water contents. 19 . i.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt.3 The Cautious start If the water content is very low. 3. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. if the polarization current changes. the titration starts so quickly that overtitration may occur. This is more suited for small water amounts. 3. The maximum dosing rate is dependent on the actual burette size. Recommendations 1. In the cautious mode. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control.4. With large amounts of water. In this case you can activate the Start: Cautious parameter. 3. The end point for a specific polarization current is influenced by the sensor and the solvent. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. the control reacts more sensitively to potential changes. which leads to a stronger reduction of the dosing speed. the end point must be adjusted. 2.g. The following points represent possible contributing factors: contaminated or old sensors. if the control band width is decreased.e. however.

• If Chloroform or Xylene is added in order to dissolve oil samples. the sensor current shall be reduced to 15 μA. instead of methanol or ethanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. the titration curve is more or less flat towards the end.g. used as solvent. This measure allows the system to cope with the reduced conductivity. this results in an illdefined titration end point. 2-propanol. the system reacts slowly in the case of ethanol based reagents. 3. the titration can be accelarated by reduction of the control band to 300 mV. the overall ionic conductivity is increased. Auxiliary reagents • If formamide is added to the solvent. table) work fine.4. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. • If 1-comp titrants are used.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. This results in a lower voltage required to maintain the polarization current. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. If 2-comp ethanolic reagents are used. e. setting up of the titrant as 1-comp KF titrant yields shorter titration times. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. 20 . Composolver E) the standard 1-Comp parameters (cf. which will lead to long titration times and to low precision. If one-component reagents are used. Ethanol-based reagents • Compared to the methanol-based reagents. the overall ionic conductivity is decreased. up to 8 mL/min for most 2-Comp 2 titrants. Therefore it is recommended to decrease the polarization current to about 15 μA.g. In order to achieve a good repeatability. • • If 1-Comp titrants are used with Ethanol (e. • If 2-comp titrants are used.

However the control band shall not exceed the start potential. 2-methoxyethanol. where the methanol has been replaced by e.g. E E t Oscillating system behaviour. Fix (400. 200. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. There is no need to accurately adjust the control band to the actual start potential. 3. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. which is the case in 1-Comp systems.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. The minimum dosing rate shall be used to fine tune the final phase of the titration. 100 mA) 21 .5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. If the titration takes too long. In most cases 300 – 400 mV are well-suited. which is the case in some ethanolic reagents. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. 3. 2.4. Cautious Generator current: Automatic. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. In general. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. an increase of the control band is recommended.6 General recommendations 1. 300.

and improved KF titration stands (i. the iodine generation is higher than in the cautious mode. high resolution burettes (0. absolute drift stop. or it can be set to a specific value (“Generator current” . During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.Fix). The closer the measured potential value from the predefined end point is. 2. relative drift stop. i. tightly sealed stand).. minimum titration time 22 . More specifically. Later on. pulse frequency and pulse height (mA) are used as variables by the instruments. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity.e. then the titration was stopped. 300. pyridine-free reagents with a faster reaction rate. In addition. a delayed switch-off time of 10 to 20 seconds was set at the end point. In particular.e. iodine is generated by means of current pulses of 400. 200 and 100 mA.g. the slope of the iodine generation rate is flat at the beginning of the titration. Variation of pulse length (time). 3.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. Normal: This iodine generation mode is generally used for all water content determinations. less than 50-100 μg water per sample). The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. Initially. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”.25 µL for a 5 mL burette). as soon as the was potential value was lower than the set end point during the defined delay time. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. Cautious: Suitable for samples of low water content (e. Five termination parameters can be defined in the titration method: delay time.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. This parameter shortens the titration time and leads to repeatable results.e. the slower is the generation of iodine. The iodine generation starts slowly. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. Since the first developed KF reagents reacted slowly. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.e. i. maximum titration time. i. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value.

g. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. After the defined time has elapsed. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. Typical absolute drift stop value: 3 µg/min (coulometric). the absolute drift stop value must be greater than the initial drift. titrant concentration (volumetric) and side reactions.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. Disadvantage: The value optimized to the initial drift.m the drift before titration) and the relative drift. Typical value for the relative drift stop = 2-5 μg/min (coulometric). The smallest increment must be sufficiently large to compensate the drift. especially if working with the KF sample oven. 23 . otherwise the termination criterion is never satisfied. Typical delay time: 5 . 15 s) following the addition or generation of iodine. • Advantage: This parameter ensures a high repeatability of the results. easy to understand (volumetric).Maximum titration time The titration is terminated after the defined time. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration.e. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. the titration is terminated and the result is printed. . Thus. otherwise the termination criterion will never be reached.

but involves a risk that the titration will be terminated a bit too early. This parameter is independent of the the initial drift (coulometric. soluble samples You should normally choose the relative drift stop as a termination parameter. The vaporization of water is also irregular in the final stages. A relative drift stop of 20 to 30 µg/min shortens the titration time. Maximum titration time for determinations with the KF drying oven When using the drying oven. so 24 . If the water content is relatively high. the drift at the end is often greater than the initial drift. It is recommended to be used for substances that release water slowly. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. i. Thus. you can ignore these traces.METTLER TOLEDO Good Titration PracticeTM in KF Titration . you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. possibly resulting in poorer repeatability and lower water contents. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability.e. and the titrant concentration (volumetric). The final traces are only extracted very slowly.6.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. 3. volumetric). This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.. Use the drift/time curve to determine this value. this is the simplest and most universal parameter to use. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. • Advantage: This parameter ensures a high repeatability of the results.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached).

If the drift is greater than 10 µg/min. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. If the drift stop value is not reached.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. It gives you the best accuracy and repeatability of results. you should take measures to reduce the drift. the maximum titration time has proven to be best termination criterion in practice. The higher drift is therefore influenced to a large extent by the sample. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. (Set the minimum titration time equal maximum titration time). the titration is terminated at the latest after the defined maximum time. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. 25 . Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. Therefore.

The air-conditioning system should therefore be equipped with a moisture condenser. Moisture can enter the sample. the greater is its influence on the results of the Karl Fischer titration. since cold air cannot absorb as much moisture. The air within the titration vessel also contains moisture. the relative humidity increases.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. whereas molecular sieves require temperatures up to 300 °C. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). it is titrated to dryness during pretitration. In this way. The following rules should be observed: • • Close all openings in the titration stand. where the relative humidity can achieve values of more than 80%.4 weeks (indicated by a colour change of the indicator of the silica gel).1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. The drift. the residual moisture dissolves more rapidly into the anolyte (solvent). The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. however. However. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. Silica gel can be regenerated over night at 150 °C. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . the titrant and the titration stand.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. the higher the atmospheric humidity in the laboratory. until it is absolutely free of water. This problem is particularly relevant in tropical climates or in coastal regions.1. Briefly. i. 26 . Do not shake too vigorously to avoid solvent gets on the cover of the vessel. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). there will be moisture on the glass surface of the titration cell and the inserts. Condition the titration cell before use. When you assemble the titration stand for the first time.3 hours. The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. This can take 1 . After the anolyte (coulometer) or the solvent (volumeter) has been added.e.

the drift value should therefore be as low as possible and stable before the start of a titration! 27 . In the standby titration. and its value is displayed on the screen. On the other hand. traces of water will always find a way into the titration cell. For accurate results. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”.(drift * titration time). or a fixed value can be defined into the titration method (“Fix value”). Therefore.1. the KF titrator continuously titrates the water that diffuses into the cell. Therefore it must be taken into account when calculating the water content. the drift indicates the quantity of water that enters the titration stand over a defined period. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . it is also possible to use the value of a previously performed drift determination (“Determination”). this water amount is also titrated during analysis. and is given in μg water/minute. On the other hand.2 The drift No titration stand is completely water tight. the last measured drift value is automatically stored. In this respect. it is necessary to quantify the amount of water entering the titration cell during titration. This is achieved by titration of the dry solvent for a defined time (drift determination).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. At the start of a sample titration. t.

However. . the level of the anolyte drops due to evaporation. 3 . By ensuring that the level of the anolyte is higher than the one of the catholyte. . If the level of the catholyte is the same or higher. which leads to a higher drift. some anolyte solutions contain an excess of iodide and the solution has a brown colour.5 cm into the electrolyte solution. . .2. As soon as the stirrer is switched off.First transfer 5 mL catholyte to the cathode compartment.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. Higher anolyte level → low drift Lower anolyte level → drift is high .The generator electrode should dip approx. This can be avoided as it follows: 1.2 Working with the coulometric KF instruments 4.When a sample is injected into the anode compartment. . 2. the level of the anolyte increases. 100 mL anolyte. you must add some methanol or sample so that the color changes to yellow.Then fill the anode compartment with approx. 28 . Note: In production.5 mm higher than that of the catholyte.Pour approx. the anolyte should be topped up from time to time with anhydrous methanol. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. the moisture enters the diaphragm and is slowly released into the anode compartment. In this case. 2. a flow occurs from the cathode compartment to the anode compartment. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. If this is not the case.1 Filling the coulometric cell • Cell with generator electrode with diaphragm . when the drying oven is used. The catholyte always contains traces of water.Make sure that the level of the anolyte is approx. • Titration cell with diaphragmless generator electrode . 100 mL electrolyte solution (anolyte) into the titration cell.Take approx. the levels slowly become the same.

In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. The capacity is monitored by the coulometers (see operating instructions). • • • • • 4. If an electrolyte is used for a long period without replacement. when using a generator electrode with diaphragm.2. . This can lead to wrong results.2. This can happen if large amounts of samples of low conductivity are titrated. e. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. If an emulsion forms in the anode compartment.g. After being used for two weeks. A level sensor in the waste bottle prevents from overflow. the level of the solvent or the anolyte exceeds the 150 mL mark. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. The higher the level in the anode compartment. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. the drift slowly increases.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. and the risk of over titration increases.Anolyte solutions (100 mL): after 1000 mg water. It is fully controlled by the titrator. . Any contact with the reagent is avoided during draining and refilling of the titration cell. With poorly soluble samples. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . If the conductivity of the anolyte drops to a very low value. below 10 μS. the worse the stirring efficiency will be. In practice.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. If the drift is too high.Catholyte solutions (5 mL): after 200 mg water.

30 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. Step 2: The Anolyte is drained into the waste bottle by applying vacuum.

Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. drying tube and tube holder enables both draining and refilling. An optional reagent exchange set consisting of tubes. In this configuration only draining of the titration cell is possible.

. If immediate use is required rinsing with anhydrous methanol shall be applied.Fill the generator electrode with anhydrous methanol. since it would cause a higher drift value. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent.This procedure should be repeated at least once.Methanol flows through the diaphragm into the cathode compartment.2. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. . Simple cleaning and drying of the generator electrode Method A: . Method B: .Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. The C30 provides a reagent monitoring routine which is called Reagent Control. which leads to a higher drift.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. . Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. especially if dirty samples are analyzed.Place the empty generator electrode in anhydrous methanol. • 32 . Moisture and contaminants are rinsed out of the diaphragm. the most effective cleaning agent is chromic acid. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. Methanol flows through the diaphragm and rinses out moisture and contaminants. Drying is not necessary if you use it immediately. The procedure is identical to that described above. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. Afterwards thoroughly rinse the generator electrode with water.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. then with anhydrous methanol and dry it as described above. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through.

2) Connect the S7 connection of the generator cell with the indication electrode. This is sufficient in most cases. samples may be deposited on the surface of the electrode. However. • With heavily contaminated electrodes. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. the indicating electrode does not need cleaning.3. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days).1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. it is better to determine the concentration every 2 to 4 hours. .g. 4. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0.5 mol/L sulfuric acid. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. The layer should therefore not be removed by cleaning. This also becomes noticeable through a dark coloration of the anolyte at the end point. the measuring electrode must be cleaned. The titrant is not chemically stable. the one-component titrant. • Clean the platinum pin with a paper tissue.if the titrant bottle is not tightly sealed. As already described.5 Cleaning the measuring electrode Generally. 4. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. 2. the tightness of the titrant bottle and the desired level of accuracy. Their volume increases considerably with temperature. e. so that there is a sharp drop in concentration.2. The Ohmic resistance of the electrode is increased. while the two-component titrant is rather stable). 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. In this case.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. 3. This leads to a higher potential jump. We recommend to determine the titrant concentration daily.if the desiccant on the titrant bottle is "used up". place the electrode in 0. In the global settings within the setup menu of 33 . repeatable results. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) .01 mg/mL per week.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. Based on the chemical stability of the titrant. This test of the complete system by a titer determination is therefore an essential condition for accurate. a layer is formed on the platinum surface after the first few titrations. which prevents a good indication.

e. Rinse the burette 2 times into a waste bottle before you determine the concentration. Make sure that nothing adheres to the beaker wall or to the electrode. 4.66% of water.3.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate. . Determine the weight by back weighing and enter it as sample size.3 to 2. Determine the concentration under the same conditions as for sample analysis. i.04 and 0. i. - 34 . which prevents the execution of further titrations.Use the optimized METTLER TOLEDO method M301 Weigh between 0. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. Na2C4H4O6•2H2O (M = 230.and at the same temperature. Mix for 3 minutes to achieve complete dissolution before you start the titration.using the same titration stand with the same volume of solvent.: . it contains 15. 2.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. 26-50 % of burette volume. This sample size yields an optimum titrant consumption of 1. Under normal conditions. The plastic tubing is not absolutely water vapor-tight. Since it slowly dissolves in methanol.08 g/mol). you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . Either the user is simply warned or the usage of the expired titrant is blocked. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic.e. Note: 1.5 mL with a 5 mL burette. Add it into the titration vessel.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.

You cannot perform more than one determinations in 40 mL of ethanol (with 0.045 g di-sodium tartrate). You must perform the determination in pure methanol! Highly soluble. They are thus protected against the ingress of moisture and can be stored for up to five years. e.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. "HYDRANAL®-Water Standard 10.05 g di-sodium tartrate dihydrate). You cannot perform more than three determinations in 40 mL of methanol (with 0. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. You can only perform one determination in 50 mL of 1:1 mixture (with 0. mixing time 1 minute. You can perform six determinations in 30 mL of Solvent* before you need to change it. 30% too high. You must either change the solvent after every sample or use pure Solvent* for the determination. This content is confirmed by the test certificate enclosed with every package. Less soluble. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. 35 .0 to 1. mixing time 2 to 3 minutes. You must perform the determination in pure methanol! Less soluble. Thus. mixing time 2 to 3 minutes.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results.g. mixing time 1 minute. Highly soluble. Partially soluble. you should weigh in 1.3.0.e. The values that are obtained are approx.3 Concentration determination with Water Standard 10. too high titer).05 g di-sodium tartrate). The values obtained are approximately 10% too high. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. mixing time 5 minutes. The water standards are supplied in glass ampoules. A cloudy solution will falsify the results (i. Partially soluble. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble. mixing time 1 minute.5 g of water standard 10. Slightly soluble.

METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e.0 mg/g water standard.01 g as the sample size.5 mL at a time as an aliquot. To reduce the influence of the atmospheric moisture. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. 3. with a Hamilton microliter syringe).g. The content of an ampoule is sufficient for 3 to 5 determinations. Start the titration without any mixing time. Thus. Use a new ampoule for each new concentration determination. Rinse a 10 mL syringe with approximately 1 mL of water standard. Glass syringes are better. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. The sample should be weighed either using a balance with a resolution of 0. Start the titration without any mixing time. 4. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. accurate results. a very good deal of practice and precise working is required to obtain repeatable.0 µL deionized water with a 10 µL syringe. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. the water content is increased and thus this will falsify the results. Inject exactly 10. You can use a water standard with 1.4 Concentration determination with pure water General When using pure water to determine the concentration. 5. 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. or with a 10.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. A balance with a resolution of 0. The error is minimized by rinsing and conditioning the syringe beforehand. Enter 0.1 mg does not satisfy the requirements for a repeatable titration.3.g. 6. – – – 36 . Plastic syringes may introduce a small amount of moisture. the whole content of the ampoule is completely drawn into the syringe. Determine the weight by back weighing. 4. Draw the whole content of the ampoule into the 10 mL syringe. Inject 1 to 1.01 mg (e. In an open ampoule the liquid standard is exposed to air moisture.

caramel. beverages Cosmetics: soaps. if it is absorbent. fat Oils: edible oil. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. the sample must release water completely. 2. After setting the volume. alcohols. You can use mixture of solvents to achieve complete dissolution. You can get rid of any bubbles in the syringe by expelling the water rapidly. Always use a syringe with a long metal shaft. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . fatty creams Waxes. Solvent Methanol Max. massage oil. to avoid touching the glass part. Insert the syringe through the 1 mm hole of the three-hole adapter. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. jelly bears Starch products: flour. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. dioxane. transformer oil. Adjust the plunger to exactly 10. diesel oil. noodles. corn.0 µL. ethereal oils Petrochemical products: gasoline. kerosene Pharmaceutical products: ointments. emulsions Petrochemical products: crude oil.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. Do not warm the syringe. tar products. Only freely available water undergoes reaction with the Karl Fischer reagent. - 4. Hold the syringe at right angles directly in front of your eyes to read off the value. ester Organic products: urea. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. However. Always add each sample in exactly the same way. suppositories Sugar products: jelly. creams.5 The solvent To determine the water content in a sample. All the screws in the syringe must be tightened securely. yogurt.3. lay it down on the adapter and empty it completely. amount 100% Samples Solvents: toluene. salicylic acid Foods: honey. it may draw water out of the needle!). hydraulic oil.

4. In this case.3. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. too low water content. The amount of formamide at 50 °C should not exceed 30%. you must replace the solvent timely. The solvent for the two-component reagent contains SO2. starch products will not dissolve in it. On the other hand. it is necessary to replace the solvent timely. and . which may be completely expended if you titrate a large number of samples with high water content. or by indicating the maximum number of samples to be titrated.salicylic or benzoic acid for basic samples. 50°C). the amount of water in mg which has been titrated. Once again. i. This will lead to incorrect results.imidazole is used for acidic samples.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. If acidic or basic samples are titrated. The extraction capacity can be improved by increasing the temperature (e. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. or the titration will take too long and titrant will be wasted. Therefore. the water will no longer be completely released. 2. 38 . 3. the titration of subsequent samples will then be very slow. formamide effectively extracts water from starch products. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. If exhausted.g. The solvents that are used should contain as few water as possible (< 100 ppm). Sugar is the only type of sample that dissolves in formamide. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: .

With liquid samples that do not dissolve water such as oils. Use bottles with a septum stopper for liquids of very low water content.e. which cannot be mixed as thoroughly as liquids. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic.the most common source of error.1 Taking the sample When taking samples for water determination. With liquid samples. In such cases. 4. the absorption or release of moisture. i. or at least minimize. you must be extremely careful to exclude atmospheric moisture . The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. the lower the amount of moisture. 39 . This can happen when a sample cools and the water solubility is decreased. 5. The sample must be representative. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. Heterogeneous water distribution in samples: In non-polar liquids. 2. such as butter. you should determine its water content as soon as possible. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. If you have to store the sample. In the case of non-polar solids. you will no longer be able to determine its true water content. you should take into account the following points: 1. the sample should be larger the more heterogeneous the distribution of the water. Use sample bottles with small openings to minimize the ingress of moisture. rinse the bottles two or three times with the sample beforehand. e. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample.g. water may be separated from the sample if it is left to stand for a long time. 3. The sample should be taken quickly to exclude. and thus air moisture can penetrate the plastic and absorbed by the sample. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. "An analysis cannot be better than the actual sample!" When sampling.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight.2 Storing the sample After you have taken the sample. it must contain the same average amount of water as the material as a whole. the water is not uniformly dispersed. oils. It floats on the surface or sinks to the bottom. 5.

Repeatable results can be obtained even with 0. 10-50 μg water can be detected if the demand for repeatability is not too high.2 1. sample size Amount of water [ppm] [g] [mg] 1 10 0. the accuracy is improved if larger sample amounts are used.0 10000 = 1% 0.0 For volumetric titrations. and the following minimum sample sizes should be used: Water content Min.5 to 17.1 to 0. This corresponds to 7. In general. it is recommended to use the minimum sample size given in the following table: Water content Min. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 .5 to 2 mg water per sample. approx. and the required accuracy and precision. the accuracy increases with the amount of sample.0 5000 0.05 mg water per sample with a titrant concentration of 1 mg/mL. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.0 1000 1 1.4 500 2 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. For coulometric analyses. Under optimum measurement conditions. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. because the absorption of air moisture during sampling and sample addition becomes less important.05 mL is thus still acceptable when using a 5 mL burette.25 100 4 0.01 10 8 0.1 to 0. A titrant consumption of 0. the optimum amount of water is in the range from 0.3 Amount of sample The amount of sample used depends on • • the expected water content.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. As a rule of thumb.08 50 5 0.1 mg water per sample. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. This corresponds to 0. For optimum accuracy with determinations in the range from 1 ppm to 1% water.1 1. If a high level of accuracy is required. the optimum amount of water is approximately 10 mg per sample.

Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 .

an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. 42 . which is accessible in the online titrations screen: Dependent on the expected water content.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. Inject it into the cell using a wide-bore needle. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. especially with samples of low water content. you must take suitable precautions to prevent atmospheric moisture from being absorbed. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. This prevents the sample from solidifying in the syringe during the weighing. honey a Waxy candle wax. silicone oil. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. suppositories b c Liquefy the sample in an oven at approx. Low water content Low water content Hygroscopic Viscous Very viscous ointments. aqueous emulsions. 43 . Possibly warm the sample slightly to lower the viscosity. In the case of a volumetric Karl Fischer titrator. paraffin. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. benzene glycerol. yoghurt. ski wax. Fill the 5 or 10 mL syringe with sample after removal of the piston. alcoholic beverages methanol. toluene. hydraulic oils. In the case of a volumetric Karl Fischer titrator.1 Liquid samples When adding liquid samples. The syringe is heated together with the wax. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. 50 °C and fill it into a syringe. edible oils hexane. creams.

Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. seal it with cotton wool and insert it into the septum bottle using a short needle. Enter the sample size in the titrator or transfer it automatically.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. Fill the syringe with sample and wipe the needle with a paper tissue. Otherwise when the syringe is removed. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". use bottles with a septum stopper and pressure equalization. To avoid this. Replace the syringe with the remaining sample on the balance and back weigh it. Start the titration. Air flows through the molecular sieve into the bottle when you take a sample aliquot. – – – – – – – – – – 44 . Fill a syringe without a plunger with molecular sieves. you must aerate the bottle with dry air (equalize the pressure). the drop will adhere to the septum. Withdraw the plunger and rinse the syringe with the sample by shaking it. If the sample is hygroscopic or has a low water content (< 1000 ppm).

salicylic acid. The sample should be quickly weighed and added to minimize air exposure. depending on the ambient humidity. Hard. e. this would lead to an error of 5% to 10%.g. chocolate.when the titration cell is opened to add the sample. 45 . jelly bears. e. With an optimum sample size of 1 mg water/sample.g. If possible.g. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. thus. For this reason. cooled analytical mill. crystalline samples: Weighing boat – Grind hard. it should be added under the same conditions as it was transported and stored.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. the storage of samples in a refrigerator may cause water to condense. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. Sample characteristic Brittle Hard/soft Pourable Procedure e. – Add the sample with a weighing boat. cellulose powder: – Either weigh the sample in a dry box or extract it externally. pulverize less hard samples in a mortar.g. jellied fruits. salts. For instance. solid fat: – Grate the product and add the sample with a spatula. about 50-100 μg water enter the anode compartment. coarse-grained samples in a closed. fatty e.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. in a volumetric KF titrator solids can be directly transferred into the titration vessel.

- 46 . ski wax.g. suppositories: – Liquefy the samples in a drying oven at approx. honey. The water content is often lower atthe surface than inside the sample. Do not use a syringe. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. – Add the sample with a spatula.g. chocolate cream. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. Add the sample into the titration vessel. Tare the balance to zero. candles. inhomogeneous e. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. fatty. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. 50 °C and fill them into a syringe. Use a weighing boat with attached flexible tubing if necessary. paraffin. Back-weigh the empty weighing boat.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. butter. Start the titration.g. because the water is released if it is pressurized Waxy e. Enter the weight in the titrator or transfer it automatically. margarine. The syringe is heated up together with the wax. to prevent the sample from adhering to the vessel wall or to the electrode.

e. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. berries: Reduce with a homogenizer in an external solvent. noodles. e. cheese: Hard. in plants) Water Example: Sugar. fatty Soft.g.g. e. sausage. e. cooled analytical mill. vegetable juices: Reduce with a homogenizer. The following methods are available: Sample characteristic Very hard Procedure e.g. e. e. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. minerals. This is not the case with solids if the water is bound as. brittle Moderately hard.g. inorganic salts.g. brittle Viscous Hard.g. coffee beans: Crush in a mixer. Fibrous natural products Suspensions 47 . suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. hard salts: Grind in a closed. grain. fruit juice extracts. dried fruit and vegetables. water adsorbed on surface capillary bounded water (e. meat. then reduce it further with a homogenizer in an external solvent. fatty Mince the product. solid fat: Grate the product.g. e.g.g. e. it is necessary to crush insoluble solids in order to gain access to the trapped water. chocolate.: • • • • entrapped water water of crystallization (salts). crystalline products: Pulverize in a mortar. jellied fruits.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. organic salts. Sample preparation Water: Example: Biological samples First of all.g.

4 0.3 1.8 1. potato chips. e.0 1. using either methanol or a mixture of it as the solvent.1 1.3 2. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.4 1. hazelnuts.9 0.g.1 4.5 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.2 1. grinding the sample additionally with a built-in homogenizer (see photos below).1 mg/pc 3.5 8.9 srel / % 0. etc.9 0.0 7. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .8 4.8 1.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. You can speed up the extraction of water from the sample by • • In many cases. sugar.4 1. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12. heating the solution with a thermostating titration beaker.

pepper.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. Briefly. In particular. water is extracted from the sample by means of a defined quantity of solvent of known water content. butter milk.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. 350 ppm) and toluene (max. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. 600 ppm). edible fat) for natural substances (almonds. 49 . Pay attention to the water capacity of chloroform (max. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. curry) for dehydrated products for sugar (total water).

For the extraction of tablets. A dilution factor of 10 . A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). - 50 . or use an ultrasonic bath with heating. Add a sufficient amount of sample.20 is normally used. Shaking is the method generally used for extraction. or use a homogenizer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. the smaller the relative error because the total error is calculated with respect to the sample size. The larger the sample. Step 3: Extraction - Shake.

Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. 51 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. % or ppm).

9 11.5 0.5 9.3 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.4 4.4 0. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .6 61.4 0.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.8 54. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.4 0.3 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.6 72. The weight of the solvent (msol).6 0.

by selecting the appropriate calculation (i. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. Note: 1. 2. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. 3. for instance. The water content of the solvent should be as low as possible.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. Chloroform. “External extraction”) in the method function “Calculation”. the formula is automatically given. reaches the saturation limit for water already at 350 ppm! 53 .e. In particular. The amount of sample should also take account of the absorption capacity of the solvent.

%: C = (VEQ*CONC-TIME*DRIFT/1000)*0. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.2 10. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. or with a high water content Pure solvents can be used to dissolve the samples.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. or with a very low water content.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent.9 5. the addition of methanol is not necessary. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. in % or ppm.2 1.8 2.

Determine the weight of anolyte injected by back weighing. the error as a result of opening the titration stand will be between 10 and 30 µg. Thus. because a large sample amount leads to a too long titration time. biological tissue. On the other hand. Draw 10 . If the solid has a low water content (<200 ppm).g. the error obtained by direct titration if the titration stand is opened to add the sample is too large. 7. Rinse the syringe two or three times in this way. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. In fact. Direct titration is not suitable. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. 5. 3. and too much titrant is consumed. Determine the weight by back weighing. serum. weigh it and inject it into the septum bottle. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. 6. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. this error is reduced. Draw an aliquot into the same syringe again. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. weigh it and inject it into the titration cell.20 mL of anolyte titrated to dryness into the syringe. Remove approx. 7. Since you are able to work with larger amounts of sample when working with this technique. 2. the blank value correction is too large compared to the amount of water in the sample. 4.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. 55 .

because the anolyte titrated to dryness has a blank value of "0". then you can additionally calculate the result can be given in ppm. If you know the lyophilized sample amount in the septum bottle. 8. Thus. 4. the water amount in the septum bottle is 4 times larger. Since ¼ of the total amount was injected. The water amount in µg is determined. 6. 7. 5. The accuracy of a plastic syringe is enough. Rinse the syringe two or three times in this way.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. 2. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. zero must be entered for the blank value (B). Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. 3. In this way. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. Remove approx. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. 56 . Alternative procedure: 1. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. With a standard method calculation and calculate the water amount in µg. the final result must be multiplied by 4 (factor f = 4).

Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. . evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations.With sample vessels the gas amount gas can be determined by differential weighing.g. . . Determination .If possible. to prevent the gas from flowing into the titration vessel. . . time" and a "Delay time" of e. to ensure that the titration is terminated after the maximum time. you must fill the gas either into special gas sample tubes or into small steel cylinders. you should titrate the gas sample directly from the source.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.As soon as the drift is stable again. water-free absorption liquid in which CO2 itself does not dissolve.5 Determination of water in gases To determine the water content of gases. hydrochloric acid.Select "Max. .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min.Turn the three-way valve. depending on the water content of the gas. 600 s as termination parameters.When titrating large quantities of gas in the same solvent. . .Stop the gas flow after 1 to 2 mL titrant has been consumed.Calculate the volume from the time and the gas flow rate. The gas must be directed through a water-dissolving. The water content in ppm is calculated by entering the volume and the density. If not. the gas must be directed through the titration vessel for a defined period of time.Purge the system with the gas before you start the determination. 57 . The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.Purge the sample vessel and the tubings thoroughly beforehand with the gas. . .g.CO2 gas can not be titrated directly since iodine reacts with CO2. Sampling/sample addition . start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. Notes .

5 . for accurate results do not select a too high gas flow rate. cause side reactions with the Karl Fischer reagent. If you use air for organic samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results. you should use a two-stage pressure regulator so that the final pressure is in the range 0.4 – 8. the oven temperature should not exceed 160 °C.6. causing the water in the sample to vaporize. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven.0 mg/L Therefore. chapter 7. the purge gases must be first dried before entering the KF oven. 58 .6.6 Determination using the drying oven This method is suitable for solids and liquids that 1.2 Purge gas Air contains oxygen. If you use nitrogen from a gas cylinder.7 500 97. or 2.: o o air with 50% humidity: approx. Air should therefore only be used for non-oxidizable.1 Principle The sample is heated in an oven. 11 mg/L nitrogen gas from a cylinder: 1. inorganic samples.4) A gas stream of approx. The water is transferred to the titration cell in a current of dry inert gas (purge gas). cf.5).6. For Karl Fischer titration. Thus.1 bar (cf.9 166 99. 7. which could react with the sample at higher temperatures. 7. chapter 7. and the amount of water is determined. e. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. that release water very slowly. The purge gases commonly used contain moisture.6.g.1 - The recovery rate is clearly decreasing with increasing gas flow rate.

7.e. in contrast to other desiccants. Silica gel can be regenerated over night at 150 °C. all the water is vaporized and transferred to the titration cell. Method 1: The water evolved is continuously titrated After a short mix time (20 . the titration starts and the released water is continuously titrated. In such cases you should use the maximum titration time as termination parameter (i. but their water absorption capacity is low. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. Silica gel is appreciably better in this respect. 100% Phosphorous pentoxide. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum. In the case of KF coulometers.6.e. deactivate the drift stop). you should set the maximum titration time as the termination parameter (i. there are two types of anolyte solutions: 59 . 2. they are rapidly exhausted.80 µg H2O/L 40 . Silica gel and molecular sieves have the advantage that they can be regenerated. especially methanol. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. In order to avoid the latter you may also use the minimum time as termination parameter. deactivate the drift stop). The KF titration is then started. whereas molecular sieves requires temperatures up to 300 °C.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell.60 s). Method 2: The water is first vaporized and then titrated afterward During a defined long mix time.e. i. At the end of the titration. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . the vaporization is often very irregular. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. To ensure that the determination is repeatable. With some samples the drift at the end of the titration is significantly higher than the initial drift. The relative drift stop or the maximum titration time can be used as the termination criterion.

time Max. An air pump is available as an optional accessory. This is particularly important with low-weight samples (e. 1 mL/hour – From time to time. time 60 . The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. fibers) or with samples of low water content.7 99.2 4. It has a large glass sample boat capable of holding up to 10 cm3 of sample. dedicated anolyte to be used with a KF Oven (e.8 6.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. Coulomat AG Oven): Anolyte loss at 150 .e. there is a small loss of water. i.g. 7.4.9 9. The recovery therefore depends on the amount of methanol vaporized and the method used. 3. Examples: Sample Result / ppm No.6.2 1.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C.5 . Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . the recovery is not 100%. time Max.2 99.9 2. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). time Max. the faster the water is titrated. you should replace the anolyte lost through vaporization with new anhydrous methanol.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. oven temperature 200 °C: approx. time Max.200 mL/min.200 mL/min. time Max. i.e.g. as well as a gas flow meter. The procedure for the determination of water content is described in the operating instructions. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99.95 98.1 Briefly: The less methanol is vaporized. Due to the vaporization of the methanol. oven temperature 200 °C: approx.5 mL/hour Anolyte containing ethylene glycol. and the better the recovery.

In such cases. If several determinations are performed in the same solvent. the recovery increases to 99. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. 2. 10.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. start the titration so that the drift value is automatically entered. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. If the drift is higher than 15 μg H2O/min. For instance. 3. Then. This leads to a too low result. and does not drop into the cathode compartment/ titration cell. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. the evaporated solvent lost in the gas stream has to be replaced. replace the silica gel and molecular sieves of the gas drying unit. To check the performance of the titrator/drying oven system. and/or replace the anolyte of the KF coulometer. purge the "cold zone". 6. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). For the same reason. Set a gas flow rate of 150-200 mL/min. 5.7%.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. bent drying tube.55% or VWR/VWR/MERCK water standard KF oven 1%. 61 9. do not select the parameter "Auto start". This can happen when the titration is started only after complete evaporation. evaporated solvent does not condense in the drying tube. If the drift is constant. Open the stop cock. Some samples have surface water that is lost as soon as the oven is purged with dry gas. in volumetric KF titration the methanol loss is approx. 4. Close the stop cock and purge the "hot zone". . A large amount of evaporated water cannot be fully absorbed by the solvent. 3. If the water is titrated as soon as it begins to evaporate. you should proceed as follows: 7. Some samples require some time before water starts evaporating. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%.

The blue rubber cap seals the sample vial tightly against the oven. including the oven temperature. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. 3. After the analysis. while a glass tube pierces the aluminum foil cover. 1 During a sample series: 2 3 1. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. 62 . The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. 2. The drying oven can be operated in the temperature range from 50 to 300°C. Besides 14 places for glass sample vials.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. The sample vials are moved upward into the oven by a lift. are included in the titration method. The oven heats the sample to the set temperature.6.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). The drift value is defined as the moisture entered into the titration cell by the purge gas. the moisture in the empty sample vial has first to be removed. To determine the drift value accurately. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. This is particularly important with light samples (e. Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack.g. This takes 10-20 minutes as can be seen in the following diagram: 63 . fibers) or with samples of low water content.

The loops run through one after the other and the samples are processed sample for sample. different plastic samples have to be analyzed. The blank value can also vary as a function of temperature.e. for example. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. Nevertheless. whose optimum bake-out temperatures differ. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. For each series. they can be measured at different temperatures using the same method.300 μg water. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. > 15 μg H2O/min). The blank value should be determined before each series because the humidity can change. suboptimum conditions. With rapidly changing.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. the blank value determination also takes the actual drift into account. the method contains a so-called sample loop. etc. To determine the blank value as accurately as possible. In this case. Performing the drift and blank value determination In general.g. It is therefore not necessary to perform a drift determination before each series. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. and thus the moisture adsorbed on the glass walls is not always the same. 64 . drift value x time). it is important to use a new sample vial for each blank value determination (i. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). If this is the case.e. If. If the maximum titration time is used as termination criterion in the method -which is what we recommend. the vial used no longer has the same properties as the "fresh" sample vials. gas flow. i. If the temperatures of successive loops are different. In the same way. At the start of the method. This means that the stored drift value of the previous determination will be used. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. In this case. moisture in the sample vial.e. The optimum blank value is in the range of 70 . Thus. one with the same properties as the sample vials into which the samples have been filled in). as well as the anolyte in a coulometric analysis. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i.e. the drift value can change with time. These method templates are based on a dedicated KF method type called ‘Stromboli’. you can check whether the drift is constant and the new drift value can be used for the next series. the moisture in the air present in the vial. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures.) are always slightly different.the analysis times for the determination of the blank value and for each sample are the same. The new blank value is automatically used for the blank correction. a blank determination can be performed between two sample loops. The first sample of the next loop is then transferred into the oven and the water determination begins. Important: After a blank value determination. By performing a drift determination at the end of the series or between several series. the moisture content is somewhat lower. you can enter the number of samples the series includes for each loop.

and therefore it does not drop into the cathode compartment. drying and storage). 6.g. A sudden shutdown of power immediately switches the valve in that way. This valve shall be used especially if inert gas sources are used. This test also serves to check the tightness of the oven and the connection tubing 65 . 2. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. 3. 8.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1.g. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. With STROMBOLI. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. bent drying tube. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. To check the titrator/drying oven system. evaporated solvent is not condensing in the drying tube. 4. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external.55% or VWR/VWR/MERCK water standard KF oven 1%. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. you can not only determine solids but also liquid samples. see also list of results). 7. Use the same vials for a sample series as well as for the blank value determination. In this way. motor oil) or completely vaporized (e. 5. These are partially vaporized (e. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. The delivery tube has a T-piece that causes a small leak flow. This has a large effect on the blank value and thus on the result. since it provides a leak free inert gas stream during normal operation. toluene. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. Set a gas flow of 40–60 mL/min.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

0 5. with decreasing sample size the relative standard deviation srel becomes worse. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. it is necessary to use the optimum sample size in order to achieve precise results. 69 .0 3. A good repeatability is achieved the sample size is increased particularly for low water content values.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs. Therefore.0 2.0 Sample size (g) In both cases.25 0.5 1.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

72

Homogenize sample. Oven: .Higher oven temperature .Replace molecular sieves and silica gel in drying tube . .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Clean titration cell and generator electrode and dry at 50 – 80 °C .Increase vaporization time.Replace anolyte Amount of sample too small .g.Check whether titration stand is completely tight. . Water distribution in the sample is not homogeneous . increase t(max) Wrong control parameters .Replace anolyte .Measurement electrode is not plugged in . if possible increase amount of sample Wrong sample preparation and sample addition .Use smaller sample Long titration time.Level of anolyte should be higher than that of the catholyte .Use higher oven temperature . titration never ends Very long pretitration Poor repeatability Wet anolyte . .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Use rel.Use a different method Oven: water not completely vaporized . especially at low water content (< 1000 ppm) 73 .Increase end point Oven: water vaporizes very slowly and irregularly .Use t(max) as termination parameter . drift stop .The repeatability is strongly dependent on suitable sample preparation and sample addition.Add a small amount of one-component KF titrant to the catholyte.Check whether titration stand is completely tight.Increase amount of sample to ensure that approx. 1 mg water per sample is present.Lengthen vaporization time (increase t max) . drift stop as termination parameter.Increase value for rel.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Grease the tapered joints Moisture from cathode compartment and diaphragm .Measurement electrode is faulty Titration stand not protected against moisture .Clean the platinum pins of the measurement electrode with paper tissue . e.

do not splash to the walls of the cell.Add sample into KF reagents. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . check generator electrode.Extend tmin (minimum titration time) Incomplete sample addition . .0.use a bigger sample size up to 0. contamination with atmospheric moisture occurs. For samples with very low water content < 30 ppm .Use smaller sample size Values too high The titration was too fast → overtitration . bad repeatability With water standard 1. It has no influence to the result.Check drift and blank value .Too low value: see above “too low value” if this does not help.3 g Generator electrode is contaminated The black cover cannot be removed. if it is defective. Checking drying oven Out of limits. Sample not dissolved (emulsion) . 10 – 15 minutes . the Coulometer must be adjusted With water Standard KF Oven 1 %.Reduce the value for rel.Replace or change the anolyte .Use higher oven temperature .0 or 0. .Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. at 170 °C.Sample not thermal stable: Use lower oven temperature .Too high value: see above “too high value” .Lengthen vaporization time (increase t max) . If the sample preparation and addition is not done carefully.Use start cautious Oven: .Replace anolyte .Use back weighing. drift stop .2 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Use fix generator current 100 mA . Anolyte has too low conductifity .Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Replace anolyte If this doesn’t help.Replace or repaire generator electrode.1 mg/g .

e.The repeatability is strongly dependent on suitable sample preparation and sample addition.Use different method.Increase endpoint potential Oven: water vaporizes very slowly and irregularly .Extend vaporization time (increase t max) .Use t(max) as termination parameter . drift stop" as a termination parameter.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker. .Homogenize sample. .Increase amount of sample to ensure 10 mg water per sample.Reduce sample size Poor repeatability of the results Amount of sample too small .Use higher oven temperature .Use "Rel.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture . Low water content (<1000 ppm)! . 75 .Grease the tapered joints Condition Titration stand .2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . e.Clean platinum pins of the electrode with a paper towel. external extraction. Wrong control parameters .g. Side reaction of the sample with the KF reagent .Check and optimize control parameters.Increase value for relative drift stop. titration never ends Wrong termination parameters .Replace molecular sieves and silica gel in drying tube .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10. drying oven. . Oven: water is not completely vaporized .Extend tmax (maximum titration time) .g.Increase vaporization time. if possible increase amount of sample. Water distribution in the sample not homogeneous .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . increase t(max) Long titration time. etc. Titration stand not protected against moisture .Check whether titration stand is completely tight.Increase oven temperature .see above Oven: .

Change solvent. Poor sample preparation and addition .4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Sample is not thermally stable: Use lower oven temperature .Check drift and blank value . Oven: .Change solvent or use fresh solvent after every sample. With water Standard KF Oven 5. Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results. contamination with atmospheric moisture occurs. 15 – 20 minutes . Di-sodium tartrate has only limited solubility In methanol max. .Extend tmin (minimum titration time) Incomplete sample addition .Replace solvent . For samples with low water content < 400 ppm .Use higher oven temperature .Replace the solvent frequently. which dissolves the sample.55 % at 220 °C. Determination of the concentration using di-sodium tartrate or Water Standard 10. No more sulfur dioxide in the solvent . bad repeatability 76 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .0 is a simpler and a more dependable method.12 g in 40 mL. drift stop .Reduce the value for rel.Reduce dVmax and dVmax factor.Add chloroform or other solvent to methanol. The concentration determination is correct only if the di-sodium tartrate has completely dissolved.Use titrant with 2 or 1 mg/mL Oven: .Use back weighing. 0.Samples of low water content (<1000 ppm) are always hygroscopic.Increase sample size up to 0.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . Sample not dissolved .Extend vaporization time (increase t max) . If the sample preparation and addition is done carefully.Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .

V4 C20 Mercaptans V0. C20 V11 C0 V2.g. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl.V5 C20 Ethers Linear and cyclic V2. naphthalene > C20 Tar. R-Br.C22 V16 C0 V10 C0 Nitrocompounds V3. indole. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.V4. bitumen V4. toluidine Oxidizable with iodine: aminophenol Method V2. C0 V2 C20 V15 Low pKa value: phenol. o-cresol Side reaction: naphthol. C0 Sulfur compounds Phenols V0.V4. C24 Hydrocarbons > C12 Biphenyl.1 Solid samples 11. R-I R-NCO Benzophenone Method V2. anthracene. e. V4 V2.: benzamide. V4 C20 V15 C20 V0. diphenylmethanol Weakly basic pKa >8: Imidazole. nitrobenzaldehyde > C12 Stearyl alcohol. C0 V2. V5 C20 V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11. salicylic acid High pKa value: 2-chlorophenol.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. V3. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. oxalic acid Oxidizable with iodine: ascorbic acid V2. V3.V5 C20. C0 Peroxides V2. cresol. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 .V5 C20.C22 V2.V3 C20 di-Nitrobenzene.V7 V2.V4.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde.V3.V4.V3.1.V8 C20 V10. nitrotoluene. V4 C20 V2. anisidine. V3. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine.V3.pyren e.

78 . V31 C20. C34 V10 Na2HAsO3 .g.1. V8 Cosmetics Creams. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . C34 V2. etc. polystyrene. NaHCO3 Na2CO3 B2O3 . polyurethane. V32 C20. Silicon dioxide Silanols R3Si(OH) Na2SO4. C32 V15. lotion Lipstick Soaps Toothpaste V4. NH4NO3 Nitrites NaNO2 11. V31 C20.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V30 Insecticides. V5 V12 V2 V40.C40 V2 Adhesives All-purpose glue. HBO3 . H3BO3 NaOH. dispersion dyes Waxes. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. Phosphate. PVC. etc. ZnSO4 V2. poly-amides. fungicides. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. KOH MgO. NaAsO2 KHCO3 . MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . V32 C21.1. paraffins: shoepolish. C32 Pharmaceuticals Antibiotics. V31 C32 V2. C34 V31 C33 V2. CaCl2 . e. KJ. Na2HPO4 tert.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. indicator dyes. V31 C20. CaO NaCl. C34 V2. V32 C21. creams Suppositories Tablets Lyophilized preparations V2 V4. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. V31 C31. V5 V5 V2 V20 V2 V5 V30. bitumen lubricating grease. polypropylene.: Na3PO4 Silicon oxide. herbicides Soluble: wool dyes. ski wax Tar. V32 C20. disinfectants Salves. multipurpose grease V2 V2. Insoluble: pigments. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21.

(V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . jellied fruits. mayonnaise Shortening. V23 Cacao. (V25) V22.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. coffee beans.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. corn. candy. almond paste Instant ice tea. instant coffee. tobacco. rye. gummi bears.4 Technical products . perborates) without brightener Total water V30 V2 11. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. tea.1. silk 11. wheat. noodles. Zwieback. dried vegetables and fruits Hazelnuts. (V30) Cheese. jelly Sugar: adherent moisture Chocolate Spices Pepper.almonds instant coffee Fats Butter. ice cream Dried albumen Powdered milk V2 V13 V2. meat spread.1. mixed spice Mustard Adherent moisture: plain salt. V23 V30. Zwieback Yogurt.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. margerine. C30 V2 V20 Paper. wood Cellulose powder Wool. hardened fat V4. potato chips Potato flakes Dough. broth Biscuits. pudding powder. noodles. jam Honey. V21 Mortar. V23 Vegetable products V22.. curry.1.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. sea salt V23 V24. sea salt Total water: plain salt. plaster. caramel. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont.

nitrotoluene. dioxane. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. cyclohexene. acetophenone. pentane. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. chinoline Strongly basic: alihatic amines N-butylamine. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. chlorotoluene Acetone. ethyl acetate Methyl chloride. crude oil. anisole Methyl benzoate. paraffin Aldehyde Acetaldehyde. acetic acid > C2 propionic acid. disulfides sulfonic acids Mercaptans V1. methylethylketone Ketones V10 C10 80 . benzene. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. chlorobenzene. toluidine. hexanol. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. xylene C7 to C14 gasoline.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. isobutane. hexylamine Reaction with methanol: aniline. C1 Sulfurcompounds V1 C1 V0.2. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. methylal C1 to C7 hexane.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal.2 Liquid samples 11. petroleum. HNO3. t-butyl chloride. dodecane > C14 heavy oil. HCl Nitrobenzene. ethylal. diamine Easily oxidized with iodine: hydrazine. cyclohexane. toluene.

fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. transformer oil. sample input and titration methods. cream. brake fluid. massage oil Vegetable oils Technical oils Hydraulic oil.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.3. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides.2. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. 81 . tinctures Cosmetics: perfume.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. refer to chapter 11. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. wine. liquor Pharmaceuticals: extrakts.

reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 . Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . In this case methanol is used as a solvent. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .3 Titration Methods 11.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .10 minutes Direct titration methanol free Titrant: two comp.1 Volumetric methods The methods have been developed using 2-component reagents.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.120 s Delay time: 7 seconds. These can be also performed using the one-component reagent.3.

15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min With drying oven at 160 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate. Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .

2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.3. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 . Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.

margarine Phenols. shoepolish Creams.g. Dissolve sample or extract water. SiO2 Salts. cristalline products Wheat. gummi bears. jelly. resinous Waxes Examples Butter. greasy Soft. rocks e. At room temp. After sample removal keep sample sealed. Pulverize with mortar.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 .g. After sample removal keep sample sealed. S3 S2. honey.4. tea. active ingredients Na-tartrate S9 S12 11. chocolate Method S1 S1. noodles.) Homogenize sample well. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. S11 S4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. coffee. S2 S1. S3 S10. brittle Soft. (Select stir time so that sample dissolves completely. for very thick pastes drill hole in bottom of syringe.: CaCO3 . S11 S6. broth Hardened fat.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. Pulverize with mixer. greasy Examples Minerals.4 Sample preparation and input 11. meat Jellied fruits. cooled analysis mill. Stir. S8 S10 Property Soft. S10 S2. Homogenize sample well. No further preparation necessary. Zwieback Dried vegetables and fruits.8 mm ) Fill in backend of syringe Procedure Grind in sealed. formamide). In external extraction solvent (methanol. shake or sonicate. Cut in small pieces with scissors or knife. ice cream. 1-decanol. meat grinder. Use grate to reduce size. almonds. S10 S11 S10. wool. pastes Pulverized soluble Salves. bitumen Method S7. (Pre-heat syringe with hair dryer or in drying oven. pepper. paper. potato flakes Tar.5 mm or without needle.) S8 S9 S10 syringe with needle Ø 0. almond paste.1 Solids: Characteristics Property Very hard Hard. 60° C. 1-decanol. Press through small holes e. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. Use syringe with needle Ø 1. creams gel. tobacco. napthalene. Inject into titration cell. formamide). Melt sample.4. yogurt Salts. silk Cheese. S5 S10 S8 Paraffins. or up to approx. Let solids settle and remove aliquot of remaining solution with syringe. S10 S11 S4.

.5 Accessories for sample input Syringe Injection needle Weighing boat.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter.Remove sample immediately.4. milk. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times. .15°C Examples Propanol. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . H2SO4.8 mm).4. . after-shave Beverages. detergents. toluene.Keep sample in a septum flask. .8 mm) Inhomogeneous emulsions .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. crude oil. acetic acid Silicon oil.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0. Boiling point 5 . 0°C in ice bath.4.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.The pressure loss during sample removal must be compensated with dried air. .Homogenize thoroughly by shaking or stirring prior to sample removal. . For each titration use 1 mL syringe (with needle Ø 0.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.Cool sample to approx. acetone.15 °C .8 mm) Injection with syringe (without or with needle Ø 1.5 mm) Injection with syringe after cooling sample (with needle Ø 0. salad oil Perfume. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. gasoline.Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. aqueous emulsions Acrylic enamels. glycerine Hexane. petroleum.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. glass Visco-Spoon™ 1 mL ME-71492 1. glycerine Acetaldehyde Methanol. Hygroscopic sample or low moisture content (< 1000 ppm) . acetone. synthetic enamels. 11.

Part II. Soc. Z. Chem. SEUBERT A. Part V. SCHOLZ.. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. “Mechanism and reaction rate of the Karl Fischer titration reaction. Rotating ring disk electrode meassurement“.S. Ind. SEUBERT A.W. WÜNSCH. Chem 368.C.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. J. “Karl-Fischer Reagentien ohne Pyridin“. 407-415 (1978). Electroanal. 312. Chem. Anal. K. 256-260 (1989) (in German). “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. Fresenius Z. Rotating ring disk electrode meassurement . Chem. Amer. Chem.6 References [1] [2] FISCHER. BARENDRECHT. Chem. Both publications from: SEUBERT.. GRÜNKE. WERNIMONT. Einkomponenten Reagentien“. 306. J. Anal. See literature references in: EBERIUS.. Anal. Fres. A. Analytical implications”. G. . Liebigs Ann.. F. COFINO. E.. 394 . E. Fresenius Z... J. 334. Auflage. G. Z.207 (1980). Anal. 75-80 (1978). E. 139-147 (2000).396 (1935).. J. 1999 (in German). “Analytical Procedures Employing Karl Fischer Reagent I. Anal. SCHOLZ. Neue Eichsubstanzen“. BOYD. 395-403 (1977). C. Chem. SCHOLZ. J. HOPFKINSON. Chim. 123-125 (1981). 16-21 (1989) (in German). Potentiometric measurements”.. Anal. Acta. VERHOFF. Verlag Chemie Weinheim (1954) / (in German). Anal. 203 . Chem. Th. M.. Zweikomponenten Reagentien mit Imidazol“. E.C. 1. 309. S.396 (1981).comparison with the aqueous system“.J.. W. E. 71.. BARENDRECHT. Anal.. Diploma-Thesis at the University of Hannover / Germany. J. M. MEYER. Part IV. Nature of the Reagent”.. E.. Fresenius Z. “Untersuchungen zur Karl-Fischer-Reaktion”. 303. 75.. Chem. 265 (1853). 86. Anal. G. Angew. W. P. Anal. J. Thesis University of Hannover.M. „Karl-Fischer Reagentien ohne Pyridin. S. “Mechanism and reaction rate of the Karl Fischer titration reaction. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. 94.. 394 . 31 (2). 48. J. „Wasserbestimmung mit Karl-Fischer-Lösung“. 334. Chem. BARENDRECHT.C. [8] SCHOLZ. 305-315 (1976). „Kinetics and stoichiometry in the Karl Fischer solution“. PhD. BRYANT. VERHOFF.C. Fres. Chem. 30-32 (1981). First and second order catalytic currents at a rotating disk electrode“... Eng. VERHOFF. Chem.. 93.. G. W. VERHOFF. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”.2412 (1939). 272 – 274 (1943). Chem.4. “Mechanism and reaction rate of the Karl Fischer titration reaction. 705-717 (1976). 215 – 219 (1959). 86. Chem. KOK. SCHOLZ. 2407 ... 309. 460-464 (1982). 61. Fresenius J.. R. Anal. [9] WÜNSCH. MITCHELL jr. SMITH. Fresenius Z. Chem. „Karl-Fischer Reagentien ohne Pyridin. „Karl-Fischer Reagentien ohne Pyridin. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. Electroanal. J. Electroanal.. Chem. [10] GRÜNKE. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. E. 15 (4). “Mechanism and reaction rate of the Karl Fischer titration reaction. BUNSEN. WÜNSCH.. Fresenius Z. J. J. [3] [4] [5] [6] [7] 87 . Ed. A. Part III. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. E. Electroanal.C. E.. D. 1988 (in German). Part I. „Mechanism and reaction rate of the Karl Fischer titration reaction. Chem. VERHOFF.

5 Additional literature HYDRANAL®-Manual.. „Untersuchungen einer Karl-Fischer-Reaktion“.Theorie und Praxis“. „Wasserbestimmung durch Karl-Fischer-Titration ..30918 Seelze / Germany. Diploma-Thesis at the University of Hannover / Germany. 11.. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications".METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. GIT Verlag GmbH.. 2006. Springer Verlag Berlin. SCHOLZ. „Eugen Scholz Reagents for Karl FischerTitration“.. G.A. M. K. E. DE CARO C. 1984. 1985. Darmstadt / Germany.. Sigma-Aldrich Laborchemikalien GmbH. D. 1989 (German) 88 . RÜEGG K. DE AGOSTINI A. WIELAND. 431-435 (2006). Food Chemistry 96. SCHÖFFSKI. „Karl Fischer Titration“..

For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. 89 . Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. WP: This is what we get from the calculation in the KF method. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). % or ppm). The sample P used for the extraction is not dissolved.

1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. Thus.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.01% VWR/VWR/MERCK APURA water standard 0. in % or ppm. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample. Total water content (sample + solvent). the total volume is increased. The sample P used for the external dissolution is completely dissolved into the solvent. 90 .3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0. Blank value (water content in% or ppm) of the solvent.

hydrocarbons (C10 to C20).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. part of the water content is not measured.4 Reagents and solvents for coulometric analysis To determine its total water content. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. Alternatively. nitrocompounds. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. etc. esters. the anolyte must be immediately replaced. acetamide.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10).e.4. A number of different anolytes are available to dissolve the various types of samples encountered in practice. ethers. alcohols. etc. the sample must completely dissolve in the anolyte.4. This means that if an emulsion is formed in the anolyte. the water content determined is lower than the actual water content of the sample. 12. This is limited to a maximum of 30% to prevent the conductivity from falling too low. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . more solvent can be added to the anolyte. chlorinated hydrocarbons (up to C10). ointments. i. If the sample does not completely dissolve. edible oils. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. In this case. an emulsion is formed.

This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low.4. we recommend the use of a second titration cell. If you measure ketones regularly. transformer oils. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. silicone oils. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. hydrocarbons (above C20). etc.4. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. For cells without diaphragm: - Notes on ketones: - - 92 . Chloroform must be added to the anolyte to ensure the solubility of these samples.

METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. etc.5 to 7 (see Section 1. Short chain aldehydes (e. the substances can. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. e. The special reagent for ketones can also be used for other samples.4. with reactive ketones such as cyclohexanone use only 0. The measurement should not be performed in the titration cell because the electrode introduces too much water. 1 mL). Aromatic aldehydes (e. the drift is higher because of the very slow side reaction. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. With Karl Fischer titrations of acidic and basic samples. benzaldehyde) can also be determined by coulometric KF titration. Use the HYDRANAL® buffer (SIGMA-ALDRICH).5 mL. - For acidic samples. easily be measured with volumetric KF determination.2). In these cases the pH value of the anolyte should be measured. i. The use of imidazole increases the pH value in the anolyte. Measure the pH with a glass electrode adjusted with aqueous buffers. The larger the sample. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. however. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. It is important to note that alcohols that react with ketones should not be titrated in this reagent. the more important the effect of side reactions becomes. Fill the anode compartment with approx. After a longer standby period. 80 mL of anolyte and 20 mL HYDRANAL® buffer. formic acid. Fill the anode compartment with approx. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).2 mL to 0. e.e. Choose relatively small samples (approx. To do this. the pH value of the anolyte must be adjusted to the range 5. amines: - 93 .: - For basic samples.g.g. - - Notes on aldehydes: - - 12. Basic samples must be neutralized with salicylic acid or benzoic acid. acetaldehyde) are oxidized at the anode with the formation of water. Coulometric KF titration cannot be used to determine these compounds. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. take an aliquot of anolyte from the titration cell.g.g. acetic acid.

A number of different anolytes are available to dissolve the various types of samples encountered in practice. esters.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. alcohols. edible oils.55% (potassium citrate monohydrate). etc. ointments.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. In this case.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10).6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. chlorinated hydrocarbons (to C10). acetamide. If it does not completely dissolve. The water content is declared on a test certificate supplied with every vial. etc.e. the anolyte must be immediately replaced.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. nitrocompounds. Alternatively. hydrocarbons (C10 to C20). ethers. the result determined is lower than the actual water content. i.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. 12. part of the water content is not measured.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. One-component reagents: 94 . One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12.6. an emulsion is formed. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. This is limited to a maximum of 50%.6. more solvent can be added to the anolyte 12. In this case.

This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.3 For samples insoluble in methanol or ethanol These include: petroleum oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. hydrocarbons (above C20). transformer oils. or an acetal. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. Chloroform must be added to the anolyte to ensure the solubility of these samples. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal.6. One-component reagents: 95 . One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water. etc.6. silicone oils. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.

5 to 7 (see Section 1. e. amines: 96 .METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents.g.g. however.2 mL to 0. It is important to note that alcohols that react with ketones should not be titrated in this reagent. the more important the effect of side reactions becomes. In these cases the pH value of the anolyte should be measured. With Karl Fischer titrations of acidic and basic samples. - Notes on aldehydes: - - 12. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. etc. Aromatic aldehydes (e. the pH value of the anolyte must be adjusted to the range 5. i.g. - For acidic samples. acetaldehyde) are oxidized at the anode with the formation of water. acetic acid. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult.: - For basic samples. easily be measured with volumetric KF determination.6.5 mL. benzaldehyde) can also be determined by coulometric KF titration. e. 80 mL of anolyte and 20 mL HYDRANAL® buffer. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. Coulometric KF titration cannot be used to determine these compounds. The use of imidazole leads to a high pH value in the anolyte.2). Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. To do this. take an aliquot of anolyte from the titration cell.e. the substances can. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). the drift is higher because of the very slow side reaction. The special reagent for ketones can also be used for other samples. If you measure ketones regularly. Fill the anode compartment with approx. we recommend the use of a second titration cell. formic acid.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. Short chain aldehydes (e. 1 mL). with reactive ketones such as cyclohexanone use only 0. Use the HYDRANAL® buffer (SIGMA-ALDRICH). Measure the pH with a glass electrode adjusted with aqueous buffers.g. Choose relatively small samples (approx. The measurement should not be performed in the titration cell because the electrode introduces too much water. The larger the sample. If you have titrated a number of ketone samples.

Health hazard when inhaled.: 87 °C Ignition temp. Keep away from open flames or sparks. Keep container tightly closed. Health hazard upon inhalation. Irritant when inhaled. Disposal: as an organic solvent.: 28 °C MAK value: 100 ppm Flammable. chloroform.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . buffer (imidazole). Safety: Highly flammable.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. Health hazard when inhaled.1 ppm. tetrachloromethane. iodine. Ignition temp. Ignition temp. buffer (imidazole) and solvent (methanol. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Safety: flammable to extremely flammable. and solvent (methanol. Do not let reagent contact skin or eyes. Keep away from open flames or sparks. Fill the anode compartment with approx.2 Two-component reagent: Composition: iodine and solvent (methanol. 13.3 Reagents for coulometry: Composition: iodine. 13. Health hazard when inhaled. sulfur dioxide. Potential teratogen.: 11 °C MAK value: 200 ppm Highly flammable. Keep container tightly closed and far removed from open flames or sparks. 13. Do not let reagent contact skin or eyes. Ignition temp. Disposal: as an organic solvent. Do not let reagent contact skin or eyes. 2-methoxyethanol). swallowed or allowed to contact skin.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. Keep container tightly closed. Irritant when inhaled. Skin irritant. Poisonous when inhaled or swallowed. 2methoxyethanol or diethyleneglycolmonomethylether). oxidant Ignition temp.: 46 °C MAK value: 5 ppm Flammable. swallowed or allowed to contact skin. 2-methoxyethanol. 2methoxyethanol or diethyleneglycolmonomethylether). Disposal: as an organic solvent.1 One-component reagent Composition: sulfur dioxide. 13 Hazards and waste disposal tips 13. poisonous when inhaled or swallowed. Safety: flammable to extremely flammable. buffer (imidazole) and solvent (methanol. Irritant when inhaled. swallowed or allowed to contact skin. The KF solvent contains: sulfur dioxide. xylene or trichloroethaylene).

Irreversible damage possible.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.: 95 °C Irritant for skin and eyes. Ignition temp. Potential teratogen. Ignition temp.: 6°C MAK value: 20 ppm Extremely flammable.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Health hazard upon inhalation 98 .

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com For more information Mettler-Toledo AG. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3.e.mt. Evaluation of the appropriate titration system (DQ) i. www. method validation.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. Routine operation including PQ. development of SOPs and maintenance of the validated state of the analytical system. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. evaluation. Switzerland Tel. ©09/2009 Mettler-Toledo AG Printed in Switzerland. specification of the analytical requirements and purchase decision 2. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. ME-51725145A Markt Support AnaChem . It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators.

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